US5569451A - Photoprotective/cosmetic compositions comprising triorganosilylated benzotriazoles - Google Patents
Photoprotective/cosmetic compositions comprising triorganosilylated benzotriazoles Download PDFInfo
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- US5569451A US5569451A US08/555,334 US55533495A US5569451A US 5569451 A US5569451 A US 5569451A US 55533495 A US55533495 A US 55533495A US 5569451 A US5569451 A US 5569451A
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- US
- United States
- Prior art keywords
- triorganosilylated
- formula
- sunscreen
- benzotriazole
- benzotriazole compound
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000002537 cosmetic Substances 0.000 title claims abstract description 27
- 230000003711 photoprotective effect Effects 0.000 title claims abstract description 17
- 150000001565 benzotriazoles Chemical class 0.000 title description 11
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 32
- 230000000475 sunscreen effect Effects 0.000 claims abstract description 31
- -1 benzotriazole compound Chemical class 0.000 claims abstract description 30
- 239000012964 benzotriazole Substances 0.000 claims abstract description 19
- 210000004209 hair Anatomy 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 8
- 230000002939 deleterious effect Effects 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Chemical group 0.000 claims description 2
- 229910052739 hydrogen Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000007764 o/w emulsion Substances 0.000 claims 1
- 239000007762 w/o emulsion Substances 0.000 claims 1
- 230000000254 damaging effect Effects 0.000 abstract description 3
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 210000003491 skin Anatomy 0.000 description 13
- 238000012216 screening Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 238000006459 hydrosilylation reaction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003925 fat Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004166 Lanolin Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- 239000003205 fragrance Substances 0.000 description 3
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- 235000019388 lanolin Nutrition 0.000 description 3
- 239000002674 ointment Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- DLAHAXOYRFRPFQ-UHFFFAOYSA-N dodecyl benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1 DLAHAXOYRFRPFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000002014 erythemogenic effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
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- 239000012467 final product Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
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- 229940066842 petrolatum Drugs 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 239000012429 reaction media Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 2
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical class CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 description 1
- CFHKBFAHALFKCJ-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methyl-6-[3-[tris(2-methylpropyl)silyl]propyl]phenol Chemical compound CC(C)C[Si](CC(C)C)(CC(C)C)CCCC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O CFHKBFAHALFKCJ-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002610 basifying agent Substances 0.000 description 1
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- 238000000861 blow drying Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940079362 emollients softeners Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 229940056211 paraffin Drugs 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000037368 penetrate the skin Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000760 phototoxic Toxicity 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000037307 sensitive skin Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- GEUFMGZEFYJAEJ-UHFFFAOYSA-N tris(2-methylpropyl)silicon Chemical compound CC(C)C[Si](CC(C)C)CC(C)C GEUFMGZEFYJAEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
Definitions
- the present invention relates to novel triorganosilane-substituted benzotriazoles and to novel cosmetic compositions for topical application comprising said triorganosilylated benzotriazoles, for the photoprotection of the skin and/or hair against ultraviolet radiation (such compositions hereinafter sometimes simply designated “sunscreen,” “sunscreen/cosmetic” or “photoprotective/sunscreen” compositions).
- UV-B irradiation causes erythema and skin burns which can impair the development of a natural tan; hence, such UV-B radiation must thus be screened from the skin.
- UV-A radiation of wavelengths of from 320 to 400 nm, which tans the skin, also adversely affects it, in particular in the event of sensitive skin or skin constantly exposed to solar radiation.
- UV-A irradiation causes, in particular, a loss in the elasticity of the skin and the appearance of wrinkles, promoting a premature aging thereof.
- Such irradiation promotes triggering of the erythematous reaction or enhances this reaction in certain individuals, and may even be the source of phototoxic or photoallergic reactions.
- UV-A and/or UV-B photoprotection of human skin
- aromatic compounds displaying an absorption of UV radiation in the region from 280 to 315 nm or in the region of from 315 to 400 nm, or else in both of these regions together.
- sunscreen compositions as oil-in-water emulsions (namely, a cosmetically acceptable vehicle, carrier or diluent comprising an aqueous continuous dispersing phase and an oily discontinuous dispersed phase) which contain, at various concentrations, one or more traditional lipophilic and/or hydrophilic organic sunscreen compounds comprising an aromatic function suitable for selectively absorbing harmful or deleterious UV radiation.
- sunscreen compounds and the amounts thereof are selected as a function of the desired specific sun protection factor (the specific protection factor (SPF) being expressed mathematically by the ratio of the irradiation time required to attain the erythemogenic threshold with the UV screening agent to the time required to attain the erythemogenic threshold in the absence of UV screening agent.)
- SPDF specific protection factor
- these compounds having anti-UV properties must also display good cosmetic characteristics in the compositions comprised thereof, good solubility in common solvents, and especially fats such as oils and greases, and also good resistance to water and to perspiration (durability).
- p-aminobenzoic acid derivatives benzylidenecamphor derivatives
- cinnamic acid derivatives cinnamic acid derivatives and benzotriazole derivatives are particularly representative.
- certain of these compounds do not display all of the properties required for an acceptable UV screening agent in sunscreen compositions.
- their intrinsic screening activity may be insufficient
- their solubility in the different formulations employed for photoprotection is not always sufficiently good (fat solubility in particular)
- sunscreen compounds of the benzotriazole type derivatives thereof have been prepared which have improved properties, especially in respect of their fat solubility and their cosmetic character, by effecting bonding of the benzotriazole screening group via grafting (hydrosilylation) onto a macromolecular chain of the silicone (organopolysiloxane) type.
- Such derivatives are described in EP-0,392,883, assigned to the assignee hereof, and are generally denominated "silicone screening agents", but the fat-solubility of these compounds can still be inadequate and, furthermore, in order to provide satisfactory sunscreen properties, it is often necessary to employ relatively large amounts of these photoprotective polymers, resulting in poor cosmetic properties in respect of the formulations comprised thereof.
- a major object of the present invention is the provision of novel triorganosilane-substituted benzotriazole sunscreen compounds which display improved properties, in particular in respect of their solubility in fats, as well as regards their cosmetic properties.
- novel triorganosilane-substituted benzotriazole sunscreen compounds are prepared which avoid or conspicuously ameliorate the above disadvantages and drawbacks of the prior art silicone sunscreens, said novel compounds displaying, in particular, very high sunscreen activity, both in the UV-A range and in the UV-B range, very good solubility in the common organic solvents and notably in fatty substances such as oils, excellent cosmetic properties, very good chemical stability (better resistance to hydrolysis both in acidic and basic media) and very good photochemical stability, rendering same particularly well suited for formulation into photoprotective/cosmetic compositions for protecting the skin and/or the hair against the damaging or deleterious effects of ultraviolet radiation.
- the present invention features novel silane derivatives of benzotriazoles having the following structural formula (1): ##STR2## in which n is an integer ranging from 0 to 3, inclusive; the radicals R 1 , which may be identical or different, are each a C 1 -C 8 alkyl radical; R 2 is hydrogen or a C 1 -C 4 alkyl radical; the radicals R 3 , which may be identical or different, are each a C 1 -C 8 alkyl radical or a phenyl radical; and p is an integer ranging from 0 to 10, inclusive.
- the bonding of the bridging structural unit --(CH 2 ) p --CH(R 2 )--CH 2 -- to the benzotriazole nucleus thus ensuring linking of said benzotriazole nucleus to the silicon atom of the triorganosilane, may be effected via any available position presented by the two aromatic ring members of the benzotriazole: ##STR3##
- This bonding is preferably via position 3 or 5 (aromatic ring bearing the hydroxyl function) or 4' (benzene ring adjacent to the triazolyl ring), and even more preferably via position 3 or 5.
- bonding of the substituent radical or radicals R 1 when present, may be effected via all other available positions within the benzotriazole. However, such bonding is preferably via position 3, 4' and/or 5.
- the alkyl radicals can be linear or branched and are advantageously selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals.
- the preferred alkyl radicals according to the invention are the methyl, ethyl, propyl, n-butyl, n-octyl and 2-ethylhexyl radicals. Even more preferably, the radicals R 1 and R 2 are methyl radicals.
- random derivatives or well-defined block compounds having at least one, and even more preferably all, of the following definitions:
- R 1 is methyl
- R 2 is a hydrogen atom or is methyl
- R 3 is methyl, ethyl, isopropyl or isobutyl
- p is equal to 1.
- silane derivatives of benzotriazoles according to the present invention include the following:
- a traditional synthesis can be employed, e.g., a hydrosilylation reaction of the type: ##STR4## starting from the corresponding triorganosilane in which the radical A is replaced by a hydrogen atom.
- organosilane derivatives containing SiH functional groups are well known compounds in the silane industry and are generally commercially available.
- R 3 has the same definition as in the above formula (1).
- the triorganosilylated benzotriazole sunscreen agents according to the invention exhibit one or more essential structural differences which are the source of their exceptional properties, namely, the fact that, on the one hand, there is only one benzotriazole moiety grafted onto a silicon-containing structural unit, and that, on the other, such silicon-containing structural unit is reduced in this instance to its simplest form, since, according to the invention, it is a monosilane.
- the compounds of formula (1) above excellent intrinsic screening activity with respect to UV-A and UV-B ultraviolet radiation.
- the compounds of formula (1) may be used in high concentrations, thereby imparting very high specific protection factors to the final compositions; moreover, they distribute themselves uniformly in standard cosmetic vehicles comprising at least one fatty phase or at least one cosmetically acceptable organic solvent, and may thus be applied to the skin or hair to form an effective protective film.
- their cosmetic properties are very good, namely, in particular, compared with the silicone screening agents of the prior art, these products are less sticky and render the skin or hair sofer.
- these products are very stable chemically (they are especially particularly resistant to degradation by hydrolysis which may occur both in acidic and basic media) and photochemically (i.e., they are also resistant to degradation induced by ultraviolet rays).
- the present invention also features cosmetic compositions comprising, in a cosmetically acceptable vehicle, carrier or diluent, preferably including at least one fatty phase or at least one organic solvent, an effective photoprotective amount of at least one compound of the above formula (1).
- the compounds of formula (1) are advantageously present in proportions ranging from 0.1% to 20% by weight, and preferably from 0.5% to 10% by weight, relative to the total weight of the composition.
- compositions of the invention may be used as compositions for protecting the human epidermis or hair against ultraviolet rays, as sunscreen compositions or as makeup products.
- compositions may, in particular, be in the form of a lotion, a thickened lotion, a gel, a cream, an ointment, a milk, a powder or a solid stick and may optionally be packaged as an aerosol, as a foam, a mousse or a spray.
- They can contain the usual cosmetic adjuvants and additives, such as fats and fatty substances, organic solvents, silicones, thickeners, softeners, emollients, complementary sunscreens, anti-foaming agents, moisturizing or hydrating agents, fragrances and perfumes, preservatives, surfactants, fillers, sequestering agents, anionic, cationic, nonionic or amphoteric polymers or mixtures thereof, propellants, basifying or acidifying agents, colorants, dyes, pigments or nanopigments, in particular those designed to provide a complementary photoprotective effect by physically blocking out ultraviolet radiation, or any other ingredient customarily used in cosmetics, especially for the production of sunscreen compositions.
- cosmetic adjuvants and additives such as fats and fatty substances, organic solvents, silicones, thickeners, softeners, emollients, complementary sunscreens, anti-foaming agents, moisturizing or hydrating agents, fragrances and perfumes, preservatives, surfactants,
- organic solvents are the lower alcohols and polyols, such as ethanol, isopropanol, propylene glycol, glycerol and sorbitol.
- the fats or fatty substances can comprise of an oil or wax or mixtures thereof, fatty acids, fatty acid esters, fatty alcohols, petrolatum, paraffin, lanolin, hydrogenated lanolin or acetylated lanolin.
- the oils may be selected from among animal, vegetable, mineral or synthetic oils and, in particular, hydrogenated palm oil, hydrogenated castor oil, liquid petrolatum, liquid paraffin, purcellin oil, volatile or non-volatile silicone oils, and isoparaffins.
- the cosmetic composition according to the invention are used for protecting the human epidermis against the deleterious or damaging effects of UV irradiation or as sunscreen compositions, they are advantageously formulated as a suspension or dispersion in solvents or fatty substances, or, alternatively, in the form of an emulsion (in particular of O/W or W/O type, but preferably of O/W type) such as a cream or a milk, or of a vesicle dispersion, or as an ointment, a salve, a gel, a solid stick or an aerosol foam.
- the emulsions may additionally contain anionic, nonionic, cationic or amphoteric surface-active agents.
- the cosmetic composition according to the invention when used for the photoprotection of the hair, they can be formulated as a shampoo, a lotion, a gel or rinse, to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or straightening of the hair, or as a styling or treatment lotion or gel, a blow-drying or hair-setting lotion or gel, a hair lacquer, a permanent-waving or hair-straightening composition, or a composition for dyeing or bleaching the hair.
- the cosmetic compositions according to the invention are used as makeup products for the eyelashes, the eyebrows, the skin or the hair, such as a skin-treatment cream, a foundation, a lipstick, an eye shadow, a blush, an eyeliner, a mascara or a coloring gel
- they can be formulated in solid or pasty, anhydrous or aqueous form, such as oil-in-water or water-in-oil emulsions, suspensions or gels.
- the cosmetic treatment of the skin or hair to protect same against the deleterious effects of ultraviolet radiation, in particular solar radiation comprising topically applying to the skin or hair an effective amount of a sunscreen/cosmetic composition as described above, or of a compound of the above formula (1).
- This compound is thus a very effective sunscreen which is active in the UV-A and UV-B range.
- reaction medium was concentrated and chromatography was carried out on silica under pressure (eluent: heptane). A fraction of the desired final product, which was in the form of a white powder having a melting point of 37° C., was thus recovered.
- UV absorption characteristics (measured in ethanol) of this compound were as follows:
- This compound is thus a very effective sunscreen which is active in the UV-A and UV-B range.
- a photoprotective/sunscreen formulation in accordance with the invention was prepared in the form of a sunscreen cream containing:
- This cream was formulated according to the standard techniques for the preparation of emulsions, by dissolving the screening agent in the fatty phase containing the emulsifying agents, heating this fatty phase to about 70°-80° C. and adding, with vigorous stirring, the water which had been heated to the same temperature. Stirring was maintained for 10 to 15 minutes and, after permitting the composition to cool with moderate stirring, the fragrance and preservative were lastly added at about 40° C.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR94-13394 | 1994-11-08 | ||
FR9413394A FR2726561B1 (fr) | 1994-11-08 | 1994-11-08 | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
Publications (1)
Publication Number | Publication Date |
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US5569451A true US5569451A (en) | 1996-10-29 |
Family
ID=9468621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/555,334 Expired - Fee Related US5569451A (en) | 1994-11-08 | 1995-11-08 | Photoprotective/cosmetic compositions comprising triorganosilylated benzotriazoles |
Country Status (17)
Country | Link |
---|---|
US (1) | US5569451A (fr) |
EP (1) | EP0711778B1 (fr) |
JP (1) | JP2885671B2 (fr) |
KR (1) | KR100217967B1 (fr) |
CN (1) | CN1052007C (fr) |
AR (1) | AR000080A1 (fr) |
AT (1) | ATE161014T1 (fr) |
AU (1) | AU679647B2 (fr) |
BR (1) | BR9504901A (fr) |
CA (1) | CA2162329C (fr) |
DE (1) | DE69501202T2 (fr) |
ES (1) | ES2113164T3 (fr) |
FR (1) | FR2726561B1 (fr) |
HU (1) | HUT73821A (fr) |
PL (1) | PL181422B1 (fr) |
RU (1) | RU2125057C1 (fr) |
ZA (1) | ZA958885B (fr) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5627227A (en) * | 1995-03-13 | 1997-05-06 | Nippon Oil Co., Ltd. | Ultraviolet absorber and coating material |
US5714134A (en) * | 1994-11-08 | 1998-02-03 | Societe L'oreal S.A. | Photoprotective/cosmetic compositions comprising benzotriazole-substituted polyorganosiloxanes/polyorganosilanes |
US5763497A (en) * | 1994-07-21 | 1998-06-09 | Shiseido Company, Ltd. | Oil-in-water type cosmetic composition |
US5843193A (en) * | 1997-03-18 | 1998-12-01 | Revlon Consumer Products Corporation | Hair dye compositions and process |
US6201000B1 (en) * | 1996-11-22 | 2001-03-13 | Ciba Specialty Chemicals Corporation | Use of selected benzotriazole derivatives for protecting human and animal skin and hair from the harmful effects of UV radiation |
US6376679B2 (en) * | 1997-12-04 | 2002-04-23 | Societe L'oreal S.A. | Photoprotective/cosmetic compositions comprising novel benz-x-azole-substituted silane/siloxane sunscreens |
US6409999B2 (en) | 1999-07-02 | 2002-06-25 | Societe L'oreal | Synergistically UV-photoprotecting benzotriazole-substituted silicon/cinnamic acid compositions |
US6677047B2 (en) * | 2000-02-04 | 2004-01-13 | Shin-Etsu Chemical Co., Ltd. | Coating composition, coating method, and coated article |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2001293708A1 (en) * | 2000-08-03 | 2002-02-18 | Ciba Specialty Chemicals Holding Inc. | Photostable, silylated benzotriazole uv absorbers and compositions stabilized therewith |
FR2818145B1 (fr) * | 2000-12-18 | 2003-11-28 | Oreal | Compositions cosmetiques antisolaires a base d'un melange synergetique de filtres et utilisations |
FR2818143A1 (fr) * | 2000-12-18 | 2002-06-21 | Oreal | Compositions cosmetiques antisolaires a base d'un melange synergetique de filtres et utilisations |
EP1900743A1 (fr) * | 2006-08-31 | 2008-03-19 | Isdin, S.A. | Dérivés organosilaniquede benzotriazoles, procédé de preparation et utilisation comme filtres UV |
EP1894936A1 (fr) * | 2006-08-31 | 2008-03-05 | Isdin, S.A. | Nouveaux dérivés de benzo-triazole, procédés pour leur fabrication, et leur utilisation en tant qu'agents de protection contre les UV |
ES2300199B1 (es) * | 2006-10-17 | 2009-06-08 | Isdin, S.A. | Nuevos derivados de benzotriazol, procedimientos para su obtencion y su utilizacion como agentes protectores de la radiacion uv. |
EP2324819B1 (fr) | 2009-11-19 | 2015-07-08 | L'Oréal | Composition parfumante colorée sans diphénylacrylate d'alkyle contenant un filtre uva hydrophile |
EP2945601B1 (fr) | 2013-01-21 | 2018-08-22 | L'Oréal | Composition cosmétique ou dermatologique comprenant une mérocyanine et un agent anti-uv à base de benzotriazole et/ou un composé bis-résorcinyl triazine |
FR3001731B1 (fr) * | 2013-02-06 | 2015-02-27 | Commissariat Energie Atomique | Nanomateriau conferant des proprietes de tenue a la lumiere |
WO2024116919A1 (fr) | 2022-11-30 | 2024-06-06 | L'oreal | Composition comprenant une grande quantité de filtre uv inorganique et filtre uv organique choisi parmi des composés organosiliciés avec un groupe benzotriazole |
FR3144753A1 (fr) | 2023-01-06 | 2024-07-12 | L'oreal | Composition comprenant une grande quantité de filtre uv inorganique et de filtre uv organique choisis à partir de composés organosiliciés avec le groupe benzotriazole |
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1994
- 1994-11-08 FR FR9413394A patent/FR2726561B1/fr not_active Expired - Fee Related
-
1995
- 1995-10-05 ES ES95402227T patent/ES2113164T3/es not_active Expired - Lifetime
- 1995-10-05 AT AT95402227T patent/ATE161014T1/de not_active IP Right Cessation
- 1995-10-05 EP EP95402227A patent/EP0711778B1/fr not_active Expired - Lifetime
- 1995-10-05 DE DE69501202T patent/DE69501202T2/de not_active Expired - Fee Related
- 1995-10-16 AU AU34237/95A patent/AU679647B2/en not_active Ceased
- 1995-10-20 ZA ZA958885A patent/ZA958885B/xx unknown
- 1995-10-30 BR BR9504901A patent/BR9504901A/pt not_active IP Right Cessation
- 1995-11-03 RU RU95119421A patent/RU2125057C1/ru not_active IP Right Cessation
- 1995-11-06 AR AR33412795A patent/AR000080A1/es unknown
- 1995-11-07 JP JP7289005A patent/JP2885671B2/ja not_active Expired - Fee Related
- 1995-11-07 KR KR1019950040154A patent/KR100217967B1/ko not_active IP Right Cessation
- 1995-11-07 CN CN95120379A patent/CN1052007C/zh not_active Expired - Fee Related
- 1995-11-07 CA CA002162329A patent/CA2162329C/fr not_active Expired - Fee Related
- 1995-11-07 HU HU9503192A patent/HUT73821A/hu unknown
- 1995-11-07 PL PL95311262A patent/PL181422B1/pl unknown
- 1995-11-08 US US08/555,334 patent/US5569451A/en not_active Expired - Fee Related
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JPH0251542A (ja) * | 1988-08-15 | 1990-02-21 | Adeka Argus Chem Co Ltd | 耐光性の改善された高分子材料組成物 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5763497A (en) * | 1994-07-21 | 1998-06-09 | Shiseido Company, Ltd. | Oil-in-water type cosmetic composition |
US5714134A (en) * | 1994-11-08 | 1998-02-03 | Societe L'oreal S.A. | Photoprotective/cosmetic compositions comprising benzotriazole-substituted polyorganosiloxanes/polyorganosilanes |
US5627227A (en) * | 1995-03-13 | 1997-05-06 | Nippon Oil Co., Ltd. | Ultraviolet absorber and coating material |
US6201000B1 (en) * | 1996-11-22 | 2001-03-13 | Ciba Specialty Chemicals Corporation | Use of selected benzotriazole derivatives for protecting human and animal skin and hair from the harmful effects of UV radiation |
US5843193A (en) * | 1997-03-18 | 1998-12-01 | Revlon Consumer Products Corporation | Hair dye compositions and process |
US6376679B2 (en) * | 1997-12-04 | 2002-04-23 | Societe L'oreal S.A. | Photoprotective/cosmetic compositions comprising novel benz-x-azole-substituted silane/siloxane sunscreens |
US6409999B2 (en) | 1999-07-02 | 2002-06-25 | Societe L'oreal | Synergistically UV-photoprotecting benzotriazole-substituted silicon/cinnamic acid compositions |
US6677047B2 (en) * | 2000-02-04 | 2004-01-13 | Shin-Etsu Chemical Co., Ltd. | Coating composition, coating method, and coated article |
US20040087711A1 (en) * | 2000-02-04 | 2004-05-06 | Shin-Etsu Chemical Co., Ltd. | Coating composition, coating method, and coated article |
US6855768B2 (en) | 2000-02-04 | 2005-02-15 | Shin-Etsu Chemical Co., Ltd. | Coating composition, coating method, and coated article |
Also Published As
Publication number | Publication date |
---|---|
ZA958885B (en) | 1996-05-09 |
HUT73821A (en) | 1996-09-30 |
EP0711778B1 (fr) | 1997-12-10 |
PL311262A1 (en) | 1996-05-13 |
CN1135486A (zh) | 1996-11-13 |
AU679647B2 (en) | 1997-07-03 |
JP2885671B2 (ja) | 1999-04-26 |
CA2162329C (fr) | 1999-02-16 |
CN1052007C (zh) | 2000-05-03 |
KR100217967B1 (ko) | 1999-10-01 |
JPH08208665A (ja) | 1996-08-13 |
FR2726561A1 (fr) | 1996-05-10 |
DE69501202D1 (de) | 1998-01-22 |
ATE161014T1 (de) | 1997-12-15 |
BR9504901A (pt) | 1997-09-02 |
FR2726561B1 (fr) | 1996-12-13 |
ES2113164T3 (es) | 1998-04-16 |
PL181422B1 (pl) | 2001-07-31 |
EP0711778A1 (fr) | 1996-05-15 |
HU9503192D0 (en) | 1995-12-28 |
AR000080A1 (es) | 1997-05-21 |
DE69501202T2 (de) | 1998-04-02 |
AU3423795A (en) | 1996-05-16 |
CA2162329A1 (fr) | 1996-05-09 |
KR960017677A (ko) | 1996-06-17 |
RU2125057C1 (ru) | 1999-01-20 |
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